A new synthetic procedure developed recently in our laboratories has made possible the synthesis of variety of new complexes of CuCN with diamines. Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. This procedure also provides an alternative pathway to a novel diamine complex reported by us previously, (CuCN)(3)(HMTA)(2) (1) (where HMTA = hexamethylenetetramine). The other diamine ligands used were 1,4-diazabicyclo[2.2.2]octane (dabco), 1,4-dimethylpiperazine (dmpip), piperazine (pip), 1,4-butanediamine (butda), N,N,N',N'-tetramethylethylenediamine (tetmen), and N-phenylpiperazine (phpip). Complex2, Cu(2)(CN)(3)(dabco-H), crystallizes in the hexagonal space group P6(3) with unit cell dimensions a = 8.174(3) Å, c = 8.083(4) Å, and Z = 2. Complex 3, (CuCN)(2)(dmpip), crystallizes in the monoclinic space group C2/m with unit cell dimensions a = 8.812(3) Å, b = 9.631(2) Å, c = 7.266(3) Å, beta = 113.40(3) degrees, and Z = 2. Complex 4, (CuCN)(2)(pip), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 9.439(3) Å, b = 10.561(2) Å, c = 8.870(3) Å, beta = 98.32(3) degrees, and Z = 4. Complex 5, Cu(2)(CN)(3)(pip-H), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 20.573(9) Å, b = 8.354(2) Å, c = 15.989(6) Å, beta = 133.70(3) degrees, and Z = 8. Complex 6, (CuCN)(2)(butda), crystallizes in the monoclinic space group P2(1)/c with unit cell dimensions a = 10.456(2) Å, b = 5.550(1) Å, c = 8.669(3) Å, beta = 106.80(2) degrees, and Z = 2. Complex 7, (CuCN)(2)(tetmen), crystallizes in the orthorhombic space group Cmc2(1) with unit cell dimensions a = 11.889(4) Å, b = 33.380(8) Å, c = 9.012(3) Å, and Z = 12. Complex 8, (CuCN)(phpip), crystallizes in the monoclinic space group P2(1)/cwith unit cell dimensions a = 17.8819(3) Å, b = 6.9190(1) Å, c = 8.6972(1) Å, beta = 96.720(1) degrees, and Z = 4.

The syntheses and crystal structures of the first cyanide, sulfur mixed ligand copper(I) complexes are reported. The first complex of the family was discovered when (CuCN)(3)(C(6)H(12)N(4))(2) (1) (C(6)H(12)N(4) = hexamethylenetetramine) was treated with aqueous thiourea. The sulfur ligands include thiourea (tu), 1,3-dimethyl-2-thiourea (dmtu), 1,3-diethyl-2-thiourea (detu), 1,1,3,3-tetramethyl-2-thiourea (tmtu), and 2-imidazolidinethione (N,N'-ethylenethiourea, etu). Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. Complex 2, (CuCN)(2)(tu)(3)(H(2)O), crystallizes in the triclinic space group P&onemacr;with unit cell dimensions a = 7.696(5) Å, b = 9.346(2) Å, c = 10.772(2) Å, alpha = 106.53(2) degrees, beta = 91.11(4) degrees, gamma = 98.42(3) degrees, and Z = 2. Complex 3, (CuCN)(3)(dmtu)(2), crystallizes in the monoclinic space group Cc with unit cell dimensions a = 10.082(3) Å, b = 14.984(5) Å, c = 11.413(3) Å, beta = 104.50(2) degrees, and Z = 4. Complex 4, (CuCN)(2)(detu)(H(2)O), crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 7.969(5) Å, b = 11.559(4) Å, c = 13.736(5) Å, beta = 100.48(4) degrees, and Z = 4. Complex 5, (CuCN)(tmtu) (polymorph a), crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell dimensions a = 8.653(1) Å, b = 9.426(1) Å, c = 11.620(3) Å, and Z = 4. Complex 6, (CuCN)(tmtu) (polymorph b), which has the same connectivity as 5, crystallizes in the triclinic space group P&onemacr; with unit cell dimensions a = 9.660(4) Å, b = 14.202(4) Å, c = 16.03(1) Å, alpha = 101.68(5) degrees, beta = 107.08(6) degrees, gamma = 70.07(2) degrees, and Z = 8. The difference between the polymorphs is that 5 has a zig-zag chain with a repeat unit of two while 6 has a 4-fold helix. Complex 7, (CuCN)(2)(etu), crystallizes in the monoclinic space group P2(1)( )()with unit cell dimensions a = 3.994(2) Å, b = 13.886(3) Å, c = 7.556(1) Å, beta = 97.07(2) degrees, and Z = 2.

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